Water-in-oil type emulsion



as I WWATER-IN-OIL'TYPE EMULSION.

' "I David X. Klein, Andover, Mass, assignor'to E. I.

' du Pont de Nemours & Company, Wilmington,

Dei.', a c'orporation of Delaware No l lrawlng. Application December 4.1940, liierial No. 713,933

' jl his invention relates to emulsions otthe teriin oil typer It .is a 'Qobject of this invention to produce stable; water-in-oil emulsions, using economic an( 1{ readily available materials. Other and furither important objects of this invention will appearasthe description proceeds.

4 Claims. (01. 252%312) this purpose for genizer.

I According to my invention, these objects are accomplished by using as. dispersing agent a polymerof a longchain-alkyl siliconic acid, which may bep're-formed or developed in situ.

TThe long-chain-alkyl' siliconic acid that I am 'speaking of is a compound which in its monom'eric state may be considered as having the forwherein Bis an alkyl radical having not less than 12 carbon atoms. ;monomer does not occur incommerce, and in- "stead one handles polymers of said siliconic acid "or of its anhydride Y (R-Sl-O-Bi-R) I of uncertain constitution.

Actually, however, the

dissolved vigorously stirred with 100 cc. oi. water. A stifi,.

The polymers are readily formed by hydrolysis "of an alkyl-silicon triester, such as the trichloride, R-SiCla; the triethoxy derivative,

r RqSi(OC2H5):i or the tri-polyglycol ester of copending application of Klein and Kvalnes, Serial No. 700,834, having the formula RSi-(QOH)3, wherein Q designates a. polymeric glycol radical as typifled by the chain radical In alllthe above formulas itis understood that R is an alkyl .radical of at least 12 carbon atoms,

.as typified by dodecyl, C12H25; octadecyl, CmHav;

gether', which; maybe achieved by hand or'in any suitable machine instance a mlcronizer or homo- My invention the following examples, it being understood that there is no intent tollmit the inventionthereby.

The parts indicated, clearly,may be varied to ativeproportions are maintained. Example 1; -Wate1 -benzene emulsion 500 cc. of a..5% solution of octadecyl silicon any optional magnitude so long as the same reltrichloride (CiaHavSiCla) in benzene was diluted,

while stirring vigorously, with 1500 cc. of water.

A still, white and very stable paste resulted which;

contained the water dispersed inthe oil. Example. 2

cc. of benzene containing .1 gm. of. CmI-IswSiCla were .diluted with 100 cc. of water while stirrin resulted.

vigorously. A stifl. stable emulsion Eznample 3.--Wate r-car b0n tetrachloride emulsion v or octadecyl, silicon trichloride were in 100 cc. of carbon tetrachloride and stable suspension resulted. I

Example 4.Water-gasoline emulsion 0.28 gm. of CmHawSiCla were dissolved .in 100 cc. of gasoline and emulsified with 100 cc. of

water. A very stiff, stable paste resulted.

Example 5.Water-lubricatmg oil emulsion 0.15 gm. ofCmHaqSiCls and 100 cc. of lubricating oil (SAE 30) were emulsified with cc. of water. A thick, stable suspension resulted.

Example 6.--Use of dodecyl silicon trichloride (CmHzsSiCls) I in place of the octadecyl silicon trichloride in Example 1 yielded a softer paste.

It will be understood that the above examples are merely illustrative, and that the details of procedure may be varied widely within the skill of those engaged in this art. Thus, in lieu of the alkyl-silicon-trichloride in the above examples, one may use the corresponding tribromide', triiodide or tri(polyglycol-200) as described in copending application, Serial No. 700,834 of myself and .Kvalnes.

The quantity of the siliconic agent may be as low as 0.02% by weight based on the total weight of the organic andaqueous phases, and as high as 3%. With the alkyl-silicon trichlorides, op-

commonly employed for will now-bef urther illustrated by 3 timum results are generally obtained by using 0.1% by weight on the above basis.

The mixing of the two phases may be effected by adding the organic liquid to the water or vice versa, and the emulsifying agent may be ins corporated initially in either phase. It has also been found operable to mix the two dissimilar phases vigorously and drop the emulsifying agent into them. However, the preferred procedure is that involving addition of water to a solution of the-silicon compound in the organic solvent.

After the emulsion is formed, or during its preparation, a neutralizing agent, ammonia for instance, may be added to remove the acidity which results from the hydrolysis of chloride atoms.

Furthermore, one may start with a pre-formed polymer of the monomeric acid (RSi0.0H) as above defined, and incorporate the same in one or the other of the phases or into a mixture of the two. In such cases, the addition of alkaline agents to the mass Becomes superfluous.

The advantages and potential uses of my invention will now be readily understood. At the present time, there are relatively few emulsifying agents which have the capacity of producing a water-in-oil type of emulsion. therefore opens upv a vast field, of possibilities in this respect, and is economical of execution. The emulsions thus produced may be used for a variety of purposes such as the incorporation of small amounts of water in fuels. for the sake of improving their combustion properties, the preparation of greases and cutting-oils containing water, preparation of polishes and creams having a stiff consistency, and manufacture of spotcleaning preparations, fire extinguisher foams, face creams, mayonnaise, etc.

In the claims below, the expression water-inoil type emulsion is to be understood as defining My invention phase.

'4' emulsions wherein water is the discontinuous phase and an oily organic liquid is the continuous and 3% based on the total weight of emulsion,

and said emulsion being free of other emulsifying agents.

2. A water-in-oii emulsion as defined in claim 1 said emulsifying agent being octadecyi-siliconic acid polymer.

3. An emulsion as specified in claim 1, the

emulsifying agent being present in quantity corresponding substantially to 0.1% based on the total weight of the emulsion.

4. An emulsion as specifledin claim 1, the organic liquid being a hydrocarbon.

' DAVID x. KLEIN.

REFERENCES orrnn The following references are of record the file of this patent:

UNITED STATES PA'I'EN'I'S Number Name Date 2,375,998 McGregor et al. May 15, 1945 2,406,671 Diamond Aug. 27, 1948 OTHER REFERENCES National Paint Bulletin, Oct;, 1945, pages 5, e, 12 and 13, "Organic silicon Polymers.

Certificate of Correction Patent No. 2,476,308. July 19, 1949.

DAVID- X. KLEIN It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows:

Column 2, line 12, for 5% read .5%; column 3, lines 39 and 40, and column 4, lines 1 to 3 inclusive, strike out the following paragraph:

In the claims below, the expression water in-oil type emulsion is to be understood as defining emulsions WiiGIGlIl Water is the discontinuous phase and an oily organic hquld 1s the continuous phase.

and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Ofi'ice.

Signed and sealed this 6th day of December, A. D. 1949.

THOMAS F. MURPHY,

Assistant Commissioner of Patents.

Certificate of Correction Patent No. 2,476,308. July 19, 1949.

DAVID. X. KLEIN It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows:

Column 2, line 12, for 5% read .5 column 3, lines 39 and 40, and column 4, lines 1 to 3 inclusive, strike out the following paragraph:

In the claims below, the expression Water-in-oil type emulsion is to be understood as defimng emulsions wherein Water 1s the discontinuous phase and an oily organic llquld 1s the contlnuous phase. a

and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 6th day of December, A. D. 1949.

THOMAS F. MURPHY,

Assistant Commissioner of Patents. 

